Process for breaking emulsions



United States Patent "ice This invention relates to the provision of a new process for resolving emulsions of the waterin-oil type.

Various liquid systems exist in industry which are in the form of water-in-oil type emulsions which must be separated into their component parts of oil and water." j

Prime example of such liquid systems are the petroleum emulsions commonly referred to as cut oil, .roily oil, emulsified oil, etc., which are obtained from producing wells, pipe lines, from the bottoms of oil storage tanks and the like, and comprise fine droplets of natu rally occurring Waters or brine s dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. Water-in-oil type emulsions are also formed under controlled conditions in processesfor removing impurities, particularly inorganic salts, from pipe line oil. Other water-in-oil type emulsions encountered in nature or industry in'-" clude gas tar emulsions, tar sand oil emulsions, emulsions encountered in the manufacture of antibiotic agents, and in the sweetening or caustic washing of hydrocarbons, and the like.

It is an object of this invention to provide a novel process for resolving, breaking or separating water-inoil emulsions into their oily and aqueous component parts. Other objects and advantages will appear as the description proceeds.

The above objects are attained by the instant invention which comprises subjecting 'water in-oil type ern'ulsions to the action of a member selected from the group consisting of polymeric vinyl ethers characterized by the formulae:

wherein R is a divalent lower allc ylene radical; R, R

and R are lower alkyl radicals; x and .y have "values of from 1 to 7; and 22 and n have values of at least 5. These polymers may be readily prepared by polymerization of a vinyl ether of the requisite alcohol, or by reacting polyvinyl alcohol with 'the requisiteflnumber of moles of the alcohol.

I 2,774,741 .iPetshfies Peslit. .95

the mono-methyl, -ethyl, -propyl, and -butyl ethers of mono-, di-, tri-, tetra-, andpenta-ethylene glycols, -propylene glycols, and butylene glycols, Z -ethylbutyl ether of ethylene glycol, and the like, or mixtures .thereof. The monomeric and polymeric vinyl ethers of these alcohols are well known 'in' the art and methods for their preparation are disclosed in U. S. P. ,No. 2,104,000.

Polymers having the type II formula given above may be broadly described as polymeric vinyl ethers of alkoxyl-alkanols and polyalkoxy-balkanols having the formula HO-CH5,(C H2eOH) PR3 B wherein R R and y have the values given above. As

representative of such alkoxy alkanols there may be. men- I tioned 3-methoxy-1-butanol, 2r-methoxy-l-hexanol, 3- ethoxy-l-butanol, 3-butoxyrl-butanol, 3,5-dimethoxy-1- hexanol, 3,5-dimethoxy-l-octanol, 3,5 -rdiethoxy-l-hexanol, 3,5,7-trimethoxy-l-octanol, 3,5,7 trimethoxydodecanol, 3,5,7 tripropoxy-l-octanol, 3,5,7,9-tetramethoxy-1-decanol, 3,5,7,9-tetramethoxydodecariol, 3,5,7,9-tetraethoxyl-decanol, 3,5,7,9,1l-pentarnethoxy-l-dodecanol, 3,5,7,9, ll-pentaethoxy-l-dodecanol, 3 methoxy '5 ethoxy lhexanol, 3,5 dimethoxy 7 propoxy -l -'octanol, 3,5-di ethoxy-7,9,1l-trimethoxy-Ldodecanol, and the like, or mixtures thereof. These alkoxy-l-alkanols and polyalkoxy-l-alkanols may be prepared by reacting, in known manner, the proper alkyl vinyl ether with an alkanol to yield the dialkyl acetal or other appropriate acetal, reacting the latter'with the same or different additional alkyl vinyl ethers, followed by hydrolysis-reduction of the reaction product. The ratio of alkanol to alkyl vinyl ether may vary from'about 2;0:l.0 to 20:1. The crude acetal which is a mixture, may then be distilled to yield individual components which may be subjected to simultaneous hydrolysis-reduction to yield. individual alkoxy alkanols as described in Examples 1, 4 and 5 of U. S. P. No. 2,618,6d3. Alternatively, the crude acetal may, if desired, be subjected to simultaneous hydrolysis reduction as described in :Example 3 of said patent and the mixture of alkanols employed as such for the pro ciuction of the polymeric vinyl ethers useful ingthe instantinvention. Mixturesof alkoxy-jl-alkanols and poly alkoxyl-alkanols may be blended in any desired proportions and the mixtures employed for etherifying polyvinyl alcohol or for vinylation and subsequent polymerization to produce the polymeric vinyl ethers useful herein.

Polymers operative 'in the instant invention have molecular weights ranging from at least 600 up to 2,000,000

. or more, Viscosity measurements are commonly used It will'be understood that in the above formulae, R, R R and R may contain the same ordifferent number of carbon'atorns andmay be branehed or straight chain. l

Polymers of the type I formula given above may be broadly described as polymeric vinyl ethers of alkoxyalkanols, alkoxyalkenoxy alkanols and alkoxypolyalkenoxy alkanols having the formula HO''(R1O)I-R wherein R R and x have the values given above. representative of such alcohols, there may be mentioned as an indication of the average molecular weight of polymeric compositions. The K value (Fikentscher) of any particular mixture of polymers is calculated from viscosity data and is useful as an indication of the average molecular weight of suchmixture. Its determination is' fully described in .Modern Plastics, 23, No. 3, l5 7 6l, 212, 214, 21 6 218 (19.45) and is defined as lQOOtimes f i ihfi emp i al re a ive viscos y ua ion: 60*

W C i i LQBQQ HUt PH-in m e h n c 'of polymer solution ands 1 isthe ratio of the viscosity Q s l o m that a pure s i nt Th K r i are reported as l000 times the calculated viscosity coefships are as follows:

Thus, when viscosity measurements are taken on solu tions which have a concentration of 1.00 gram of polymer per deciliter of solution at 25 C. (C=1), the relationing a 3-methoxybutyl vinyl ether polymer having a specific viscosity of 0.25, corresponding to a Fikentscher K value of 30.5, at various strengths for demulsification of a crude oil emulsion obtained from the oil fields at Hastfl ==v1 +l 5 ings, Texas. For these tests the amount of demulsifier Relative viscosity=specific viscosity plus one. Relative dlsclosed m the column of the table was added to viscosity: 1 o.ooizr+o.oouo'zsx= (1+o.oo1sx 1 100 ml. of crude 011 emulsion.

Hence I 7 The admixture, in capped 4-ounce round bottles, was

r 77 +10 o 00 1 go751 (1. i g 1 Relative mechanically shaken for 30 minutes. After removal, the ciisity s ecific viscosit and K are dimensionless whereas 10 bottles were allowed to stand qmescent forls minutes inhernfviscosit y Color of sample and any water separation were noted. y The bottles were then immersed in a water bath at 140 rei F. (60 C.) for 10 minutes, water separation being noted. I f C 7 These were then returned to the mechanical shaker for and intrinsic viscosity (the limit of inherent viscosity as 15 another 10 mlllutes, removed and allowed to Stand 1 0 approaches Zero) have the dimensions f dilution, e cent for 15 minutes. Color and water drop were noted; the reciprocal of concentration. Intrinsic viscosityand The bottles were then h y g y WlI'llng the V are intended to be independent f concentration contents to break a webbing that forms in the water layer. The instant invention may' be put into practice for P the table, helghtfs of the f and 011 Y F d l ifi ti i l i d i a l i l ll timeters, and the concentration of demulsifier 1S given in proportion of an agent of the type described above into Parts P mlulon P- P- Table Amount of Demulsifier Used Shaking Min- Standing 157 Min- Heated 140 F. forlO Shaking 10 Minutes (Color) utes Minutes utes, Standing 15 Swirled 1 Minutes Concentration=15 p. p. m.; 0.15 ml. of a 1% by Wgt. Dark Greenish N0 appreciable Oil 4.1, Dark Green; 4.0, Dark Green; Clear.

(Xylene50) (Isopropyl Aleohol50) Solution. Brown. separation. gag? 2.9, Very 3.0, Very Webby.

e Y. Concentration: 15 p. p. m.; 0.15 ml. of a 1% by wgt. Cocoa "do 0114.1,Greenish Brown; 4.1, Dark Green; Do.

isopropyl Alcohol Solution. 7 giaaebr 2.9, Very 2.9, Very Webby.

'8 y. Coneentration=50 p. p. m.; 0.5 m1. of a 1% by wgt. Dark Green 2. d Oil 4.2, Dark Green; .do Do.

(Xylene50) (Isopropyl Alcohol50) Solution. 7 gage; 2.8, Very e y. Coneentration=100 p. p. m.; 1.0 ml. of a 1% by wgt. lo Oil 4.1, Dark Green; 4.0, Dark Green; Do.

(Xy1ene50) (Isopropyl Alcohol50) Solution. "gag? 2.9, Slightly 3.0 Webby.

. Goncentration=l00 p. p. m.; 1.0 ml. of a 1% by wet. d0 do -do Do. Isopropyl Alcohol Solution.

1 Water layers become clear of webbing after swirling. 2 Becomes dark green in about 5-10 minutes. 1 Becomes dark green in about 2 minutes.

,the various types of apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, preferably with application of heat, and allowing the mixture to stand quiescent until the undesirable water content of the emulsion separates and settles from the mass. Slight agitation in the Water layer at this point is helpful in breaking a webbing that sometimes forms. The agent may be added directly or it may be first dissolved in or diluted with any suitable liquid medium to produce a concentrate or the like. As suitable solvents and diluents there may be mentioned water, petroleum hydrocarbons, benzene, toluene, xylene, aliphatic alcohols such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, ;octyl alcohol, mixtures thereof, and the like. Said agent may be employed as the sole demulsifier or it may be employed in admixture with other suitable well known types of demulsifying agents. The solubility of the agent in the oil or water of the emulsion to be treated is not particularly important in view of the very small amounts em-. ployed. Thus, concentrations of agent of the order of from about 10 to 100 parts per million (p. p. m.) by vol- This invention has beendisclosed with respect to certain preferred embodiments, and various modifications and variations thereof will become obvious to the person skilled in the art, It is to be understood that such modifications and variations are to be included within the spirit and purview of this application and the scope of the appended claims.

I claim:

1. A process for breaking a water-in-oil type emulsion comprising subjecting such emulsion to the action of a polymeric vinyl ether characterized by the formula 3 References Cited in the file of this patent ume in the emulsion are usually suflicient although concentrations outside of this range may in some cases be UNITED STATES'PATENTS.

effective and economically feasible. 2,104,000 Reppe et al. Dec. 28, 1947 Thefollowing table shows the results obtained in test- 2,618,663 

1. A PROCESS FOR BREAKING A WATER-IN-OIL TYPE EMULSION COMPRISING SUBJECTING SUCH EMULSION TO THE ACTION OF A POLYMERIC VINYL ETHER CHARACTERIZED BY THE FORMULA 